Citation: Yuanyuan Zhao, Zhiming Zhu, Liang Li, Bingyao Shi, Ziyang Li, Yuyang Huang, Lijun Jiang, Chao Shu. Photoinduced site-selective thiosulfinylation of alkynols for the synthesis of oxathiolene oxides[J]. Chinese Chemical Letters, ;2025, 36(10): 110900. doi: 10.1016/j.cclet.2025.110900 shu

Photoinduced site-selective thiosulfinylation of alkynols for the synthesis of oxathiolene oxides

Yuanyuan Zhao ^{a, 1} ,
Zhiming Zhu ^{a, 1} ,
Liang Li ^{b, 1} ,
Bingyao Shi ^a ,
Ziyang Li ^a ,
Yuyang Huang ^a ,
Lijun Jiang ^{b, *,} ,
Chao Shu ^{a, c, *,}

a.
State Key Laboratory of Green Pesticide, Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, CCNU-uOttawa Joint Research Centre, College of Chemistry, Central China Normal University, Wuhan 430079, China
b.
Hubei Key Laboratory of Genetic Regulation & Integrative Biology, School of Life Sciences, Central China Normal University, Wuhan 430079, China
c.
Key Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Normal University, Wuhu 241002, China

lijunjiang@ccnu.edu.cn

chaoshu@ccnu.edu.cn

Received Date: 7 October 2024
Revised Date: 12 January 2025
Accepted Date: 23 January 2025
Available Online: 27 January 2025

Figures(6)

Oxathiolene oxides are a significant class of bioactive compounds with promising implications in drug discovery, serving as bioisosteres/analogues of 2(5H)-furanones and 1, 3-propene sultones. However, existing methods are quite inadequate in their synthesis. Here, we introduced an innovative approach for the photoinduced, site-selective thiosulfinylation of alkynols, providing access to a diverse range of highly functionalized oxathiolene oxides through energy transfer followed by a radical chain process. This procedure efficiently maintains the catalytic cycle under mild and operationally simple conditions, offering excellent functional group tolerance and streamlining the synthesis of bioactive scaffolds and their derivatives that are often challenging with alternative approaches. Preliminary evaluation of live-cell cytotoxicity of oxathiolene oxides toward the 4T1 cancer cells was conducted, suggesting a potentially useable in chemical biology. The strategy presented in this study is not only mechanistically robust but also demonstrates broad versatility in late-stage functionalization, indicating its great potential application in organic synthesis and medicinal chemistry.
- Sulfinylation,
- Sultines,
- Disulfides,
- Alkynols,
- Oxathiolene oxides
1. [1]
  D.C. Dittmer, M.D. Hoey, The Chemistry of Sulfinic Acids, Esters, and Their Derivatives, Wiley, New York, 1990, p. 239.
2. [2]
  P. Vogel, M. Turks, L. Bouchez, et al., Acc. Chem. Res. 40 (2007) 931–942. doi: 10.1021/ar700096h
3. [3]
  O.B. Bondarenko, L.G. Saginova, N.V. ZyK, Russ. Chem. Rev. 65 (1996) 147–166. doi: 10.1070/RC1996v065n02ABEH000204
4. [4]
  L. Yang, Y. Li, C. Shu, Acta Chim. Sin. 82 (2024) 171–183. doi: 10.6023/A23100435
5. [5]
  Y. Zhang, H. Li, X. Yang, P. Zhou, C. Shu, Chem. Commun. 59 (2023) 6272–6285. doi: 10.1039/d3cc01238g
6. [6]
  J. Yu, X. Jiang, Ad. Agrochem. 2 (2023) 3–14. doi: 10.1016/j.aac.2022.12.003
7. [7]
  S. Yolka, E. Dunach, M. Loiseau, et al., Flavour Fragr. J. 17 (2002) 425–431. doi: 10.1002/ffj.1120
8. [8]
  D.W. Roberts, D.L. Williams, Tetrahedron 43 (1987) 1027–1062. doi: 10.1016/S0040-4020(01)90041-9
9. [9]
  T.W. Kensler, J.D. Groopman, T.R. Sutter, T.J. Curphey, B.D. Roebuck, Chem. Res. Toxicol. 12 (1999) 113–126. doi: 10.1021/tx980185b
10. [10]
  J. Zhang, X. Wang, P. Wang, et al., Sci. China Chem. 67 (2024) 908–913. doi: 10.1007/s11426-023-1814-2
11. [11]
  D.V. Smil, F.E.S. Souza, A.G. Fallis, Bioorg. Med. Chem. Lett. 15 (2005) 2057–2062. doi: 10.1016/j.bmcl.2005.02.056
12. [12]
  M.A. Franks, E.A. Schrader, M.E. Welker, Med. Chem. 13 (2005) 2221–2233.
13. [13]
  S. Kumari, A.V. Carmona, A.K. Tiwari, P.C. Trippier, J. Med. Chem. 63 (2020) 12290–12358. doi: 10.1021/acs.jmedchem.0c00530
14. [14]
  M.E. Welker, S.V. Torti, F.M. Torti, et al., US Patent 6242478, 2001.
15. [15]
  E. Thoumazeau, B. Jousseaume, F. Tiffon, J.G. Duboudin, Heterocycles 19 (1982) 2247–2250. doi: 10.3987/R-1982-12-2247
16. [16]
  S. Braverman, Y. Duar, J. Am. Chem. Soc. 105 (1983) 1061–1063. doi: 10.1021/ja00342a073
17. [17]
  F.W. Von Rein, H.G. Richey Jr, Org. Chem. 20 (1969) 32–35. doi: 10.1016/S0022-328X(00)80078-9
18. [18]
  J.G. Duboudin, B.J. Jousseaume, Org. Chem. 168 (1979) 233–240. doi: 10.1016/S0022-328X(00)83279-9
19. [19]
  C.K. Prier, D.A. Rankic, D.W.C. MacMillan, Chem. Rev. 113 (2013) 5322–5363. doi: 10.1021/cr300503r
20. [20]
  A.R. Nathan, D.A. Nicewicz, Chem. Rev. 116 (2016) 10075–10166. doi: 10.1021/acs.chemrev.6b00057
21. [21]
  G.E.M. Crisenza, P. Melchiorre, Nat. Commun. 11 (2020) 803–806. doi: 10.1038/s41467-019-13887-8
22. [22]
  R. Cannalire, S. Pelliccia, L. Sancineto, et al., Chem. Soc. Rev. 50 (2021) 766–897. doi: 10.1039/d0cs00493f
23. [23]
  V. Srivastava, P.K. Singh, P.P. Singh, J. Photochem. Photobiol. 50 (2022) 100488. doi: 10.1016/j.jphotochemrev.2022.100488
24. [24]
  M. Krumb, L.M. Kammer, R. Forster, C. Grundke, T. Opatz, ChemPhotoChem 4 (2020) 101–104. doi: 10.1002/cptc.201900231
25. [25]
  J. Yang, D. Xie, H. Zhou, et al., Org. Chem. Front. 5 (2018) 1325–1329. doi: 10.1039/c8qo00056e
26. [26]
  C. Wang, Y. Xu, Y. Zhou, et al., Org. Chem. Front. 10 (2023) 4972–5027. doi: 10.1039/d3qo00933e
27. [27]
  C. Shu, A. Noble, V.K. Aggarwal, Nature 586 (2020) 714–719. doi: 10.1038/s41586-020-2831-6
28. [28]
  C. Shu, R.S. Mega, B.J. Andreassen, A. Noble, V.K. Aggarwal, Angew. Chem. Int. Ed. 57 (2018) 15430–15434. doi: 10.1002/anie.201808598
29. [29]
  H. Li, Y. Zhang, X. Yang, et al., Angew. Chem. Int. Ed. 62 (2023) e202300159. doi: 10.1002/anie.202300159
30. [30]
  C. Shu, A. Noble, V.K. Aggarwal, Angew. Chem. Int. Ed. 58 (2019) 3870–3874. doi: 10.1002/anie.201813917
31. [31]
  M. Liu, X. Ouyang, C. Xuan, C. Shu, Org. Chem. Front. 11 (2024) 895–915. doi: 10.1039/d3qo01929b
32. [32]
  F. Jung, M. Molin, R. Van Den Elzen, T. Durst, J. Am. Chem. Soc. 96 (1974) 935–936. doi: 10.1021/ja00810a059
33. [33]
  J.L. Charlton, T. Durst, Tetrahedron Lett. 25 (1984) 5287–5290. doi: 10.1016/S0040-4039(01)81585-9
34. [34]
  R.F. Heldeweg, H. Hogeveen, J. Am. Chem. Soc. 98 (1976) 2341–2342. doi: 10.1021/ja00424a060
35. [35]
  F. Jung, J. Chem. Soc. Chem. Commun. (1976) 525–526.
36. [36]
  T. Durst, J.D. Finlay, D.J.H. Smith, Chem. Soc., Perkin Trans. 1 (1979) 950–952.
37. [37]
  Q. Shi, P. Li, Y. Zhang, L. Wang, Org. Chem. Front. 4 (2017) 1322–1330. doi: 10.1039/C7QO00152E
38. [38]
  G. Leonel, I. Klann, D.F. Back, et al., Chem. Eur. J. 29 (2023) e202202847. doi: 10.1002/chem.202202847
39. [39]
  H.W. Du, M.S. Liu, W. Shu, Org. Lett. 24 (2022) 5519–5524. doi: 10.1021/acs.orglett.2c01915
40. [40]
  Y. Luo, Handbook of Bond Dissociation Energies in Organic Compounds, CRC Press, Boca Raton, FL, 2003.
41. [41]
  F. Dénès, M. Pichowicz, G. Povie, P. Renaud, Chem. Rev. 114 (2014) 2587–2693. doi: 10.1021/cr400441m
42. [42]
  Y. Shen, H. Zhu, L. Deng, et al., ACS Appl. Mater. Interfaces 16 (2024) 56073–56081.
43. [43]
  H. Zhang, Y. Zhong, L. Yang, et al., Mol. Catal. 564 (2024) 114255.
44. [44]
  H. Zhu, Y. Zhang, G. Ren, et al., Chem. Commun. 59 (2023) 1050–1053. doi: 10.1039/d2cc06107d
45. [45]
  N.J. Beeton, S. Carver, L.K. Forbes, J. Theor. Biol. 462 (2019) 466–474. doi: 10.1016/j.jtbi.2018.11.033
46. [46]
  Y. Wang, C. Wang, Q. Tian, Y. Li, J. Agric. Food Chem. 72 (2024) 15077–15091. doi: 10.1021/acs.jafc.4c02096
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